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The Ag/Ag 3 PO 4 composites with various shapes (spheres, polyhedral, and microcubes) were synthesized by a facile precipitation method and a subsequent light-reduction route at room temperature. The as-prepared Ag/Ag 3 PO 4 composites were characterized in detail by X-ray diffraction, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, scanning electron microscopy, UVvis diffuse reflection, and photoluminescence spectroscopy. The growth processes of different morphologies Ag/Ag 3 PO 4 composites are also discussed. The decomposition test of rhodamine B (RhB) indicated that the Ag/Ag 3 PO 4 composites enhanced the photocatalytic performance compared with pure Ag 3 PO 4 , which was attributed to the surface plasmon resonance (SPR) of Ag nanoparticles and the stability of the photocatalysts. Moreover, uniform cubes of Ag/Ag 3 PO 4 showed the highest photocatalytic activity and could completely degrade RhB in 7 min, which could be primarily ascribed to the cubic structure of Ag/Ag 3 PO 4 with strong visible-light absorption and efficient separation of the photo-generated electrons and holes. Furthermore, the possible photocatalytic mechanism is also discussed.